Ethanol → Ethyl 6-(hydroxymethyl)pyridine-3-carboxylate

HRID 1976775Notes

Reaction equation

HRID 1976775 reaction equation
[Cl-].[Ca+2].[Cl-].[BH4-].[Na+].[N:6]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[CH:9]=[CH:8][C:7]=1[C:16]([O:18]C)=O.[Cl-].[NH4+].[CH2:22](O)C>C1COCC1>[OH:18][CH2:16][C:7]1[CH:8]=[CH:9][C:10]([C:12]([O:14][CH2:15][CH3:22])=[O:13])=[CH:11][N:6]=1

Participants

7

Reactant 5

HCID 702EthanolHCID 25517Ammonium ChlorideHCID 234911Dimethyl 2,5-pyridine dicarboxylateHCID 4311764Sodium borohydrideHCID 5284359Calcium Chloride

Product 1

HCID 15045504Ethyl 6-(hydroxymethyl)pyridine-3-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A slurry of dry calcium chloride (22.7 g, 0.205 mol) in ethanol (300 mL) and THF (300 mL) at 0° C. was treated portionwise with sodium borohydride (15.5 g, 0.41 mol), stirred for 2.5 hours, treated with dimethyl 2,5-pyridinedicarboxylate (20.0 g, 0.103 mol), stirred for 20 minutes, treated with saturated ammonium chloride solution (100 mL), and concentrated. The concentrate was dissolved in dichloromethane, and the solution was washed sequentially with saturated ammonium chloride solution, water, and brine, dried (MgSO4), filtered,and concentrated to provide the desired product containing approximately 10% methyl 6-hydroxymethylnicotinate. This mixture was used directly in the next step without further purification.

Workup

  1. stirringstirred for 20 minutes
  2. concentrationconcentrated
  3. dissolutionThe concentrate was dissolved in dichloromethane
  4. washthe solution was washed sequentially with saturated ammonium chloride solution, water, and brine
  5. dry with materialdried (MgSO4)
  6. concentrationfiltered,and concentrated

Sources & evidence

ORD record
ord-061f4de197b745a9b43fae80c00c7f94
Source dataset
uspto-grants-2001_05
Patent number
US06228868B1

Reaction notes

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